Continuous exploitation of fossil energy, gas and oil, has led to a demand for materials which have both high corrosion resistance and sufficient mechanical strength to stand up to the conditions they encounter, but also which are very malleable so that they can be easily transformed using existing techniques to produce pieces which may have complex shapes which necessitate handling several tonnes of these materials, for example "Christmas trees" or offshore well heads, pump bodies, or valves.
The types of corrosion encountered in the fossil energy extraction field, can be classified into three categories: the first, into which the majority of cases fall, being corrosion by CO.sub.2 gas; the second, which is quite frequent, being corrosion by a combination of CO.sub.2 and H.sub.2 S gases; and the third class of corrosive environments, which is still in the minority since it is encountered in deep wells, being corrosion by simultaneous concentrations of highly aggressive substances H.sub.2 S, CO.sub.2, and chloride salts mixed with water, methane, and hydrocarbons. These hydrocarbons can sometimes be in a minor proportion in extracted mixtures which are rendered highly acidic by the presence of H.sub.2 S and its chemical reactions.
The increase in pressure and temperature with depth renders these environments even more aggressive against metallic materials: deep wells drilled onshore and offshore in northern USA, in Europe, and in Australia, for example, have experienced high rates of corrosion and premature breakage of ordinary metallic materials. Offshore drilling adds to that the external corrosion of pieces by seawater.
The combination of such very severe conditions means that the materials used must have very good resistance to corrosion in all of its forms. However, generalised corrosion resistance is relatively easy to obtain, and it is necessary to ensure that precautions are taken against localised corrosion, stress corrosion in chloride environments, and against hydrogen embrittlement. Although the oil industry has few corrosion problems in terms of frequency, it encounters just the specific problems described above during offshore production, combined with difficulties in overcoming or evaluating actual deaeration of hot corrosive environments, which are highly acidic and under pressure, and which can lead to stress corrosion cracking (SCC) of usual alloys such as stainless steels. Stress corrosion must be distinguished from hydrogen embrittlement which is connected with the presence of H.sub.2 S, although those two mechanisms can occur simultaneously.
Among metallic materials, alloys based on Ni--Cr systems and Ni--Fe--Cr systems are used under such conditions because of the excellent compromise they offer between corrosion resistance and cost compared with other, more costly materials such as titanium. Ni--Cr based alloys with a high nickel content are known to be sensitive to hydrogen, and the severe conditions described above thus direct the choice to Ni--Fe--Cr alloys which have a high iron content which also limits materials costs.
Ni--Fe alloys with nickel contents of over about 40% by weight can be protected against stress corrosion in chloride environments in limited circumstances which depend on complementary additions, in particular of the elements chromium, molybdenum and copper.
In general, nickel based alloys containing the elements Mo, Cu and Fe are suitable for non oxidising corrosive environments, in particular non aerated environments: the synergistic effect of molybdenum and copper is recognised for countering corrosion in reducing acidic environments which are rich in chlorides, the effect of the molybdenum being preponderant.
However, in the most severe oil industry environments described above, which can be partially, temporarily, or even accidentally, oxidising or aerated, chromium, an element which resists oxidation makes an essential contribution to the corrosion resistance of Ni--Fe--Cr--Mo--Cu alloys.
The molybdenum content has a marked effect on alloys containing at least 40% of nickel and 20% of chromium, as regards stress corrosion in oil industry environments containing CO.sub.2, H.sub.2 S, Cl.sup.- and elemental sulfur. Three important criteria can be distinguished in these environments: temperature, acidity, and chloride concentration. In particular, increasing the molybdenum content can increase the maximum service temperature above which stress corrosion occurs.
Similarly, raising the molybdenum content means that higher acidity and higher chloride concentrations can be tolerated, with due allowance being made for localised corrosion of Ni--Fe--Cr--Mo--Cu alloys.
With the aim of satisfying the demand for good mechanical characteristics and creep strength, Ni--Fe--Cr based alloys exist which are precipitation hardened by precipitation of phases which confer high strength while ductility remains good. In the majority of these alloys, used in particular in the aircraft industry in the hot zones in engines or in turbines, the elements niobium, titanium, and aluminum, in suitable proportions, participate in hardening reactions by which the alloy attains its hardness during an aging treatment carried out in a temperature range where those addition elements are supersaturated in the austenitic matrix, which has previously been homogenised at a higher temperature, and which then becomes a metastable solution.
French patents FR-A-2 154 871 and FR-A-2 277 901 indicate that elements Al, Ti and Nb which are supersaturated in austenite form intermetallic compounds with nickel which produce the desired hardening, of which there are two types. Aluminum causes the formation of a face centered cubic phase with crystallographic structure L.sub.12 with an A.sub.3 B type chemical composition where A represents nickel and a small fraction of the other elements of the austenitic matrix (iron, cobalt, chromium, . . .) and B represents aluminum; that phase is termed the .gamma.' phase. Titanium can substitute all or part of the aluminum in the .gamma.' phase and can increase its hardening effect at higher temperatures.
Niobium causes the formation of an intermetallic phase with a Do.sub.22 type centred tetragonal structure, also with a composition A.sub.3 B where this time B represents niobium, the phase being termed the .gamma." phase.
Such alloys are hardened by precipitation of one or other of those phases, or both at once, between 600.degree. C. and 800.degree. C., which constitutes an improvement claimed in FR-A-2 154 871 which is applied to Ni--Fe--Cr based alloys comprising 15% to 25% by weight of iron, 15% to 25% of chromium, 2.5% to 9% of molybdenum, 1.5% to 6.5% of niobium and/or tantalum, 0.5% to 1.5% of titanium, 0.3% to 1.5% of aluminum and 0.03% to 0.2% of carbon. The alloys claimed in that patent are characterized by very precise titanium, aluminum, and niobium (+tantalum) contents, such that their sum in atomic % must be in the range 4% to 6% and such that the (Ti+AI)/(Nb+Ta) ratio of the sums in atomic % is over 0.8, with the precise aims firstly of obtaining good precipitation hardening during an aging cycle carried out in two temperature stages, and secondly of suppressing the overaging effect which occurs in such alloys during high temperature service, and finally to provide good ductility both at room temperature and when hot, for example in creep.
The invention described in FR-A-2 154 871 is based on the following discovery: the claimed properties are due to a particular and very stable morphology of the .gamma.' and .gamma." precipitates in which the six faces of the cubic .gamma.' phase precipitates formed during the highest temperature aging stage are covered with precipitates of platelets of the .gamma." phase formed during the second temperature stage, at a lower temperature than the first.
According to that invention, simultaneous precipitation of carbides in the grain boundaries can further increase the strength at high service temperatures.
European patent EP-A-0 262 673 claims a precipitation hardened nickel based alloy which is resistant to hydrogen embrittlement and to corrosion in chloride media containing H.sub.2 S. That alloy contains 15% to 25% by weight of Cr, 5% to 28% of Fe, 6% to 9% of Mo, 2.5% to 5% of Nb, 0.5% to 2.5% of Ti, up to 0.5% of Al and 54% to 64% of Ni: the claims are directed towards applications in oil industry environments. Supplementary conditions give more precise values for the alloying element contents. The alloys described in EP-A-0 262 673 do not include the addition of copper, or copper addition is limited to less than 1%, but they can be hardened by precipitation of two phases: .gamma.' then .gamma.".
EP-A-0 247 577 claims another nickel based alloy which is precipitation hardened by .gamma.' and .gamma." phases and which is resistant to corrosion in media containing H.sub.2 S and Cl.sup.- at high temperatures; that alloy contains 16% to 24% of chromium, 7% to 12% of molybdenum, less than 4% of tungsten, 2% to 6% of niobium, less than 1% of aluminum, 0.5% to 2.5% of titanium, 0 to 3% of copper, less than 20% of iron, more than 55% of nickel and controlled amounts of carbon, cobalt, silicon, manganese, boron, zirconium, nitrogen, phosphorous and sulfur. Further, the sum (Cr+Mo) is limited to 31% by weight while the sum of the atomic percentages of elements Nb, Ti and Al is kept between 3.5% and 5%.
All of the alloys described in the patents referred to above, in addition to high strength and good corrosion resistance, are easy to work and are insensitive to precipitation of harmful intermetallic phases.
However, manufacturers of pieces from such alloys and from super-alloys in general, whether involved in smelting, forging, or using heat treatment units, encounter insurmountable problems with ingots and semi-finished products weighing several tonnes and with large cross sections.
Typically forging produces pieces by thermo-mechanical transformation of ingots: for nickel based alloys containing the elements titanium, aluminum, or chromium, which have a high affinity for oxygen, ingots are produced in two steps. The first step is the production of electrodes under vacuum and the second step is one or more remelting steps using electrodes using vacuum arc remelting (VAR) or electroslag remelting (ESR). Those two remelting processes affect the quality of the metals by completing primary production (complementary purification and improving inclusion cleanliness); they also affect solidification control by reducing defects and minimising segregation of the alloying elements.
The ESR process currently results in better desulfuration, and is used especially for the production of large ingots where it is irreplaceable. Controlling the remelting parameters can produce the best structural homogeneity in the ingots.
However, as the quantity of alloying elements which are prone to segregation increases, and when the size of the remelted ingots increases, which is possible nowadays with furnaces with ever larger diameters, the risk of defects on solidification grows: defects which can occur in remelted ingots are listed in American Standard Test Method ASTM A604.
There is an absolute limit on the size of a remelted ingot for a given alloy and once the remelting parameters have been optimised, above which the degree of segregation is such that the properties in service can no longer be guaranteed at all points in its volume. The hardening elements titanium, aluminum, and niobium are known to be very limiting as regards the maximum diameter of ingots if a no-defect situation is desired.
In extreme cases, once solidification has finished, segregation of alloying elements generally causes the formation of particular eutectoid or eutectic compositions the nature of which depend on the segregated elements: niobium forms Laves phases with iron (Fe.sub.2 Nb), in which silicon is concentrated; molybdenum produces a p phase (Ni.sub.7 Mo.sub.6) with nickel, and the sigma phase with chromium and iron, while titanium and aluminum produce massive Ni.sub.3 (Ti,Al) type eutectic compositions. Further, all of those elements can form nitrides, carbides, or borides in the presence of nitrogen, carbon, and boron respectively.
Such compositions are harmful since they produce heterogeneous properties in the alloy and fix the alloying elements in the service and forging temperature ranges. Further, the majority have low melting points, which limits the homogenisation and forging temperatures of the ingots.
A further very constricting phenomenon of too much addition of elements titanium, aluminum, niobium, and molybdenum is heat hardening of a solid solution (Mo, W, Nb) or premature precipitation hardening of secondary phases (Ti, Al) which increases as the temperature falls: such hardening effects are such that thermo-mechanical transformation operations require energy which is not available with existing tools in the case of large ingots. This phenomenon limits the forging range to a minimum temperature below which the metal is too hard.
Increasing the addition of alloying elements thus has the effect of reducing the range over which alloys can be subjected to thermo-mechanical transformation, both at low temperatures and at high temperatures.
Finally, when alloys require solution heat treatment and rapid quenching followed by age hardening by precipitation of secondary phases, the size of pieces is again limited, and above that size the rate of cooling during rapid quenching is insufficient at the core of the piece to avoid the onset of coarse and disordered precipitation of the hardening phases: the addition of more alloying elements, which accentuates matrix supersaturation, accelerates precipitation kinetics which are thus out of control and thereby reduces the maximum size of pieces that can be treated.